Alpha-hydroxy-beta-fluoro-beta, beta dichloro-ethyl phosphonic acid, o, o-diester



United States Patent 0 F 9 Claims. (Cl. 260-953) The present invention relates to particular phosphonic acid 0,0-dialkyl esters having valuable pesticidal properties and to compositions containing the same, as well as the production and use thereof.

It is an object of the present invention to provide particular phosphonic acid 0,0-dialkyl esters which possess valuable pesticidal properties.

It is another object of the present invention to provide such phosphonic acid 0,0-dialkyl esters which possess especially effective insecticidal properties, rendering the same useful as pest control agents, especially in plant protection.

It is still another object of the present invention to provide esters of the foregoing type which are compatible with plants, whether used alone or in admixture with a carrier vehicle.

It is a still further object of the present invention to provide a process for the production of such phosphonic acid 0,0-dialkyl esters which is versatile and which provides good yields of the desired product.

It is a still further object of the present invention to effect the production of such esters at room temperature or at temperatures slightly thereabove in the presence preferably of inert organic solvents.

It is a still further object of the present invention to provide compositions containing esters of the foregoing type in admixture with a carrier vehicle, such as a dispersible liquid or a dispersible solid, for use in plant protection procedures.

It is still another object of the present invention to provide methods of use of such phosphonic acid 0,0-

dialkyl esters, especially in connection with the combating of pests.

It is still another object of the present invention to provide methods of combating pests which contemplate applying to such pests, including in particular insects, and 5 especially those found in plant crops, pesticidally effecwherein R and R', which may be the same or different, are alkyl radicals, preferably containing 1 to 4 carbon atoms, and optionally halogen-substituted, possess valuable pesticidal properties.

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Furthermore, it has been found in accordance with the present invention that compounds of the above-noted general formula are obtained smoothly and in very good yields when monofluorodichloroacetaldehyde is reacted with 0,0-dialkyl phosphites of the general formula in which R and R are the same as defined above.

The versatile reaction in accordance with the present invention may be illustrated by the following equation:

(III) wherein R and R have the same definitions as noted above.

Typical examples of 0,0-dialkyl phosphites which may be reacted in accordance with the present invention, for example, include 0,0-dimethyl, 0,0-diethyl, O-methyl- O-isopropyl, O-methyl-O-butyl, and O-methyl-O-(fi-chloroethyl) phosphites, and the like.

The monofluorodichloroacetaldehyde (B.P. 56-57" C.) also required as starting material for the process according to the present invention, is know from the literature. Such compound, shown by Formula III above, can be obtained in known manner by the reduction of monofluorodichloroacetic acid, for example, by means of lithium aluminum hydride, as the artisan will appreciate.

The reaction according to the present invention is carried out expediently in the presence of an inert organic solvent, such as benzene, chlorobenzene or dioxan; the monofiuorodichloroacetaldehyde and the particular 0,0- dialkyl phosphite being used in equimolar amounts and the reaction temperature preferably being substantially between about 20-50 C. After evaporation of the solvent, the so-prepared reaction product usually remains in the form of a non-distillable, colorless oil.

Among the inert organic solvents which may be used for carrying out the instant reaction are aromatic hydrocarbons, such as unsubstituted and halo-substituted mononuclear aryl hydrocarbons, and especially those having 6 ring carbon atoms, such as benzene, toluene, xylene, monoand di-chloro benzenes, and the like, and cycloaliphatic ethers, and especially C C cyclic ethers, such as dioxan, furan, tetrahydrofuran, and the like.

The compounds which are obtained by the process according to the present invention are characterized advantageously by outstanding pesticidal, especially insecticidal, properties. Such compounds possess about the same effectiveness as the known u-hydroxy-pLfi,fl-trichloroethylphosphonic acid 0,0-dialkyl esters described in US. Patent No. 2,485,578 and in the published documents of German patent application No. F 9,944. The instant compounds, however, are surprisingly very well tolerated by plants.

These significant properties of the compounds according to the present invention may be seen from the following experimental results which are set forth, of course, only by way of illustration and not limitation.

Example 1 To produce a preparation of an active compound, 1 part by weight of the active compound is mixed with 3 parts by weight acetone and 1 part by weight of emulsifier on the base of an alkylarylpolyglycol ether and the concentrate is diluted with water to the concentration given in Table 1 below. w

3 4. Tomato, cabbage and cotton plants are sprayed until tionally with the use of emulsifying agents and/or disdripping wet with the preparation so prepared. The treated persing agents, whereby, for example, in the case where plants then remain under the climatic conditions set forth water is used as diluent, organic solvents may be added in Table 1. After 8 days, evaluation of the tests is carried 5 as auxiliary solvents (cf. Agricultural Chemicals, March out by determining the degree of damage. For assessing 1960, pages 35-38). The following may be chiefly conthe degree of damage, represents an entirely healthy sidered for use as carrier vehicles or assistants for this plant and represents 100% plant damage, while interpurpose: solvents, such as aromatic hydrocarbons (for mediate values represent corresponding intermediate reinstance, benzene, toluene, xylene, etc.), halogenated, sults. 10 especially chlorinated, aromatic hydrocarbons (for in- The following specific results were obtained: stance, chlorobenzenes), parafiins, (for instance, pe-

TABLE 1 Active Temperature 28 0., relative Temperature 28 0., Active compound compound atmospheric humidity 75%: Degree relative atmospheric (constitution) concentration of damage tohumidity 85%: Degree in percent of damage to cotton Tomatoes Cabbage Cotton (CHriOME -CIH-CFClz 0. 5 0.75 1. 0. 5 0.5

(CH:O)2]I?(|JH-C C13? 0. 5 1. 5 3. 25 2. 0 3.0

1 According to the present invention. 2 Known.

As may be seen from Table 1, the instant active com- 25 troleum fractions), chlorinated aliphatic hydrocarbons pound surprisingly possesses much greater compatibility (for instance, methylene chloride, etc.), alcohols (for inwith plants than the analogous known compound, difierstance, methanol, ethanol, propanol, butanol, etc.), ing from the instant compound by a terminal trichloroethers, ether-alcohols (for instance, glycol monomethyl methyl group as opposed to a terminal rnonofluoro-diether, etc.), amines (for instance, ethanolamine, etc.), chloromethyl group. Thus, with respect to tomatoes, amides (for instance, dimethyl formamide, etc.), ketones cabbage and cotton at 75% relative atmospheric humidity, (for instance, acetone, etc.), and water; dispersible finely the compound or-hydroxy-B-fiuoro-B.fi-dichloroethyl-phosdivided solid carriers, such as natural ground minerals phonic acid 0,0-dimethyl ester, typically representative (for instance, kaolins, alumina, silica, chalk, i.e., calcium of compounds covered by the present invention, possesses carbonate, talc, kieselguhr, etc.), and synthetic ground such an effectiveness that very little damage is done to minerals (for instance, highly dispersed silicic acid, sil1- healthy plants treated with such compound. In contrast cates, e.g., alkali silicates, etc.); emulsifying agents, such thereto, much greater damage occurs with the use of as non-ionic and anionic emulsifying agents (for instance,

the known compound ot-hydroxy-fi,fi,/8-trichloroethylpolyethylene oxide esters of fatty acids, polyethylene phosphonic acid 0,0-dimethy1 ester. Specifically, a 50% oxide ethers of fatty alcohols, alkyl sulfonates, aryl suldecrease in damage occurs in the tomatoes treated, which fonates, etc., and especially alkyl aryl-polyglycol ethers,

may be fractionally stated as /2 of the previous damage magnesium stearate, sodium oleate, etc.) and dispersing experienced. As to the cabbage treated, a 62% decrease agents, such as lignin, sulfite waste liquors, methyl celluin damage is experienced using the compound of the 1058,

present invention as opposed to the known compound. As will be appreciated by the artisan, the active com- As to the cotton treated, a 75 decrease in damage is pounds according to the instant invention may be present experienced, using the compound of the present invention in such formulations or compositions in the form of mixas opposed to the known compound, whereby to demontures with one another and with other known active substrate that only A of the damage with the known comstances, if desifed- Pound c rs when using the instant compound. Regard- In general, the compositions or formulations contain ing 85% relative atmospheric humidity, the damage to Substantially between abOllt and 95 Percent y Weight cotton treated with the instant compound is A; that where f t a tive compound, and preferably substantially bethe known compound is used, which amounts to an 83% n about and 90 Percent y decrease in damage. Such high decreases in damage to The Substances according to the invention y be plants treated with a compound of the instant type as P y y themselves as the artisan will appreciate, in the opposed to the analogous known compound prove h form of their compositions with solid or liquid dispersible singular wide plant or crop compatibility and tolerance 5 carrier vehicles or other known compatible active agents, coupled with good effectiveness of compounds coming of in the form of Particular dosage Preparations for p within the scope of the present invention as opposed to Cific application made therefrom, such as solutions, m lknown compounds. That the instant compounds would siohs, suspensions, p p and granulates, which possess such outstanding compatibility and tolerance for are thus reiidy for use. plants at comparative levels of pesticidal effectiveness as The following Production example is given for the opposed to the closely analogous known compound is P p of illustrating, While n limiting, the Present completely surprising. ,vention.

Due to their outstanding insecticidal action and ex- Example 2 cellent plant compatibility, the compounds according to (011,0),P-CII-CFC]:

the present invention are extremely useful as pest control agents, especially in plant protection, preferably in ad- 0 OH mixture with a solid liquid diluent or carrier. A solution of 13 g. monofluorodichloroacetaldehyde in The active compounds according to the instant inven- 100 l, benzene is mi ed at 22 C, with 11 g. 0,0-dition can be utilized, if desired, in the form of the usual methyl phosphite. During the addition, the temperature formulations or compositions with dispersible carrier veof the mixture rises slightly. The reaction mixture is subhicles, such as solutions, emulsions, suspensions, emulsisequently heated to boiling temperature for a short period fiable concentrates, spray powders, pastes, soluble powof time and then evaporated under reduced pressure ders, dusting agents, granulates, etc. These are prepared (100-10 mm. Hg). There remain 22 g. of a-hydroxy-flin known manner, for instance by extending the active fluoro [3, 8 dichloroethyl phosphonic acid 0,0 diagents with solvents and/or dispersible solid carriers opmethyl ester in the form of a colorless oil.

Analysis-Calculated: C, 19.9%; H, 3.32%; P, 13.75%. Found: C, 19.91%; H, 3.58%; P, 12.90%.

The outstanding insecticidal effectiveness of such compound may be seen from the test results set out in the following table:

Systemic action after application Example 3 6.5 g. monofluoro dichloro acetaldehyde are added dropwise to a solution of 7 g. methyl O isopropyl phosphite in 50 ml. benzene. Subsequently the solution is heated to boiling temperature for a short time and then evaporated under reduced pressure. There remain 11 g. or hydroxy ,3 fiuoro [3,13 dichloro ethyl phosphonic acid 0 methyl O isopropyl ester.

Example 4 P-CH-C F C12 /II E Example 5.Plutella test Solvent: 3 parts by weight of dimethylformamide.

Emulsifier: 1 part by weight of alkylarylpolyglycol ether.

To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with the stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration. Cabbage leaves (Brassica oleracea) are sprayed with the preparation of the active compound until dew moist and are then infested with caterpillars of the diamond-black moth (Plutellamaculipennis).

After specified periods of time, the degree of destruction is determined as a percentage: 100% means that all the caterpillars are killed whereas 0% means that none are killed.

The active compounds, their concentrations, the evaluation times and the results obtained can be seen from the following Table 3.

TABLE 3 [Phytopathogenic insects] Active Killing rate Compound ingredient in percent after in percent days CHQO O ll 0. 1 100 POlI-CFC1 0.01 100 C C Ia-C Hz-O 0 H C H3O (H) P-CH-CFClz 0.1 100 0. 01 100 iSO-CaHrO O H Example 6.Drosophi1a test Solvent: 3 parts by weight of dimethylformamide.

Emulsifier: 1 part by weight of alkylarylpolyglycol ether.

To produce a suitable preparation of active compound, 1 part by weight of the active compound is mixed with a stated amount of solvent containing the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

1 cc. of the preparation of the active compound is applied with a pipette to a filter-paper disc of 7 cm. diameter. The wet disc is placed in a glass vessel containing 50 banana fruit flies Drosophila melanogaster) and covered with a glass plate. After the specified periods of time, the destruction is determined as a percentage: 100% means that all the flies are killed whereas 0% means that none are killed.

The active compounds, their concentrations, the evalu ation times and the degree of destruction can be seen from the following Table 4:

TABLE 4 [Phytopathogenie insects] Active Killing rate in Compound ingredient percent after in percent 24 hours PCHCFC12 0. 1 100 1 0. 01 100 1SO-C3H7O O H H 0.1 100 PCHCFOI1 0.01 100 0. 001 C ClaC Hz-O OH The procedure of Example 2 is repeated, using respectively: 0,0-diethyl phosphite and O-methyl-O-n-butyl phosphite, and the corresponding a-hydroxy-fi-fluoro-fl, fl-dichloroethylphosphonic acid 0,0-dialkyl ester is formed, i.e. 0,0-diethyl ester and O-methyl-O-n-butyl ester as the case may be.

Each of these esters possesses outstanding insecticidal effectiveness against a variety of pests, and especially caterpillars, flies, aphids, and the like, yet such compounds possess excellent plant compatibility whereby plants treated therewith are not significantly damaged, if at all. Such plants contemplate, of course, the usual agricultural crops, such as tomatoes, cabbage, cotton, and the like.

Accordingly, the present invention contemplates a versatile process for the production of 0,0-dialkyl esters of phosphonic acids having the general Formula I noted hereinabove, in which R and R each respectively is selected from the group consisting of alkyl and halo-alkyl radicals, which comprises reacting an 0,0-dialkyl phosphite having the Formula II noted above, in which R and R each respectively has the foregoing meaning, with monofiuorodichloroacetaldehyde, whereby the corresponding 0,0-dialkyl ester of phosphonic acid is formed in particularly high yields. Such reaction may be carried out in the presence of an inert organic solvent as aforesaid, such as a member selected from the group consisting of aromatic hydrocarbons, halogenated aromatic hydrocarbons, cyclo aliphatic ethers, and mixtures thereof, the reaction being carried out at a temperature substantially between about 2050 C.

Thus, 0,0-dialkyl esters of phosphonic acid are contemplated herein as valuable pesticidal compounds which have the general formula C1-C alkyl-O or have the general formula halo-C1C4 alkyl-O or have the general formula halo-(h-Ci alkyl-O (H) OH P-CH-C F 01;

C -C alkyl-O Typical compounds coming within the purview of the present invention include a-hydroxy-fi-fluoro-5,fi-dichloroethyl-phosphonic acid 0,0-dimethyl ester; a-hydroxyfl-fluoro-;9,B-dichloroethyl-phosphonic acid 0,0-diethyl ester; or hydroxy fi-fluOrO-fl,fl-dichloroethylphosphonic acid O-methyl-O-isopropyl ester; et-hydroxy-fi-fiuoro-fi,,B- dichloroethyl-phosphonic acid O-methyl-O-butyl ester; ahydroxy fi fiuoro-Bfi-dichloroethyl-phosphonic acid methyl-O-(fl-chloroethyl) ester, and the like.

The foregoing compounds advantageously lend themselves to use in pesticidal compositions in admixture with a dispersible carrier vehicle of the foregoing type, with the 0,0-dialkyl ester of phosphonic acid being present in a pesticidally effective amount, and in an amount which may be generally 01-95% by weight of the mixture with the carrier vehicle.

Furthermore, a method of combating pests is particularly contemplated herein, which comprises applying to such pests and their habitat a pesticidally effective amount of 0,0-dialkyl ester of phosphonic acid of the type defined hereinabove either alone or in admixture with a dispersible carrier vehicle.

Generally, with regard to the foregoing formulae, R and R' each respectively contemplates an alkyl radical, especially a lower alkyl radical, and particularly C -C alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, and the like; as well as a halo alkyl radical, especially a halo lower alkyl and particularly halo-C C, alkyl, including mono-, di-, tri-, and polychloro, -bromo, -iodo, and -fiuoro substituted alkyl, as well as mixed mono-, di-, tri-, and polychloro, -bromo, -iodo, and -fiuoro substituted alkyl, such as the corresponding mono-, di-, tri-, and polychloromethyl, -chloroethyl, -chloro-n-propyl, -chloro-isopropyl, -chloron-butyl, -chloro-isobutyl, -chloro-sec.-butyl, -chloro-tert.- butyl, the corresponding mono-, di-, tri-, and polybromomethyl, bromo-ethyl, -n-propyl, -isopropyl, -n-butyl, -iso 'butyl, -sec.-butyl, -tert.-butyl, the corresponding mono-, di-, tri-, and polyiodo-methyl, -ethyl, -n-propyl, -isopropyl, -n-butyl, -isobutyl, -sec.-butyl, -tert.-butyl, the corresponding mono-, di-, tri-, and polyfiuoro-methyl, -ethyl, -n-propyl, -isopropyl, -n-butyl, -isobutyl, -sec.- butyl, -tert.-butyl, dichloro-monobromo-methyl, chlorobromo-n-propyl, dibromo-dichloro-isobutyl, and the like.

In particular, the a-hydrxy-fi-fluoro-B,fl-dichloroethylphosphonic acid-0,0-dialkyl esters include the symmetrical dimethyl and diethyl esters as well as the asymmetrical methyl-isopropyl, and methyl-butyl esters as well as the asymmetric methyl-fi-chloroethyl-ester.

As used herein, i.e., both in the specification and claims, the term dialkyl ester(s) of phosphonic acid contemplates both symmetrical and asymmetrical alkyl hydrocarbon groups, as well as halo-alkyl groups, and mixed alkyl hydrocarbon and halo-alkyl groups.

It will be appreciated that the instant specification and examples are set forth by way of illustration, and not limitation, and that various modifications and changes may be made without departing from the spirit and scope of the present invention which is to be limited only by the scope of the appended claims.

What is claimed is:

1. 0,0-dialkyl esters of phosphonic acid having the general formula P-CH-CFCh in which R and R each respectively is selected from the group consisting of alkyl and haloalkyl radicals.

2. 0,0-dialkyl esters of phosphonic acid having the general formula 3. 0,0-dialk1yl esters of phosphonic acid having the general formula halO-Cr-Cs alkyl-0 O OH P-CH-C F C I:

l1al0-CiC4 alkyl-O 4. 0,0-dialkyl esters of phosphonic acid having the general formula 5. a-Hydroxy- B-fiuoro 13, 6-dichloroethyl-phosphonic acid 0,0-dimethyl ester.

6. a-Hydroxy-p-fiuoro p,fi-dichloroethyl phosphonic acid 0,0-diethy1 ester.

7. a-Hydroxy- B-fluoro 19,18-dichloroethyl-phosphonic acid O-methyl-O-isopropyl ester.

8. a-Hydroxy fl-fiuoro 13,;8-dichloroethyl-phosphonic acid O-methyl-O-butyl ester.

9. a-Hydroxy fi-fiuoro ;9,fidichloroethyl-phosphonic acid O-methyl-O-(fl-chloroethyl) ester.

References Cited UNITED STATES PATENTS 2,579,810 12/1951 Fields 260-953 2,701,225 2/1955 Lorenz 260-953 2,818,366 12/1957 Birum 167-22 2,906,661 9/1959 Baker 167-22 3,053,876 9/1962 Malz 260-461 3,059,017 10/1962 Dever 260-461 CHARLES B. PARKER, Primary Examiner.

A. H. SUT'TO, Assistant Examiner. 

1. O,O-DIALKYL ESTERS OF PHOSPHONIC ACID HAVING THE GENERAL FORMULA 